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Article history: The flux of liquid water through Nafion membranes of different thickness and equivalent weight was mea-
Received 3 October 2011 sured as a function of hydrostatic pressure and temperature. Hydraulic water transport across Nafion
Received in revised form 4 December 2011 membranes increases with temperature and equivalent weight of the Nafion. Hydraulic permeability
Accepted 5 December 2011
increases with temperature due to both decreased water viscosity and increased hydrophilic volume
Available online 13 December 2011
fraction. Convective flow from the applied hydrostatic water pressure is an order of magnitude greater
than the estimated diffusive water flux associated with the water activity gradient. Water sorption and
Keywords:
hydraulic permeability data predict a hydrophilic pore network with hydrophilic domains 2.5 nm in diam-
Hydraulic permeation
Nafion
eter spaced 5.5 nm apart. The pore network structure from water sorption and hydraulic permeability
Pore network are consistent with the spacing between hydrophilic domains observed with small angle X-ray scattering
experiments.
© 2011 Elsevier B.V. All rights reserved.
0376-7388/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2011.12.004
Q. Duan et al. / Journal of Membrane Science 392–393 (2012) 88–94 89
Fig. 1. Schematic of flow cell for water convection through Nafion membranes.
Table 1
Nafion membrane hydraulic permeabilities and water sorption.
water flux (Qw ) vs. pressure (P) for the different samples and dif- increase in water sorption between saturated vapor and liquid, and
ferent temperatures. Membrane permeabilities (kw ), defined by Eq. an additional small increase between saturated liquid at 20 ◦ C and
(1), were calculated from the flux data and are given in Table 1. The 100 ◦ C. The characteristic scattering length increases slightly with
membrane permeability is expected to be independent of water increased water content in the membrane.
viscosity, , and membrane thickness, tm .
kw 4. Discussion
Qw = P (1)
tm
The mechanisms of water transport in Nafion and structure
The results indicate that the three membranes with the 1100 of the “water channels” have been a source of intense interest
equivalent weight, N115, N1110 and N212, all had similar perme- over the past 25 years. Modeling efforts have examined different
abilities circa 4 × 10−16 cm2 at 23 ◦ C. N1035, with an equivalent contributions of water sorption and transport including diffusion
weight of 1000, had permeability about 40% greater than the and convection. Eikerling and co-workers have considered various
1100 EW Nafion. The permeability of N115 membranes increased driving forces for convection including external pressure gradient,
with temperature. Since kw corrects for the viscosity change with capillary pressure, osmotic pressure, and elastic forces associated
temperature, the data show that the permeability increased with with membrane deformation [28–31]. Experiments have lagged
temperature. behind the modeling efforts for water transport and only recently
The saturation uptake of water into the Nafion membranes have experimental results been published that provide details
(reported as = number of water molecules sorbed per sulfonate of transport resistances [1,4,5,10,20,32,33], mechanical properties
group) are shown in Table 1. The saturation water volume increased [34,35] and water profiles [36–39] as functions of water activity and
modestly with increasing temperature. The saturation water vol- temperature. These recent experimental results can be compared
ume at 23 ◦ C was also larger for the 1000 EW Nafion (N1035) than with previous modeling efforts to improve the understanding of
the 1100 EW Nafion. (Even though was the same for N115 and structure–property relationships in Nafion.
N1035 the water volume fraction is larger for N1035 because the Water permeation, water sorption and SAXS studies of water in
density of sulfonic acid groups is greater for N1035.) Nafion have been reported in the literature [18]. It is well estab-
Small angle X-ray scattering results for four different Nafion lished that water sorption in Nafion is accompanied by a strong
1110 samples are shown in Fig. 4. More detailed studies can be scattering peak with a characteristic distance of ∼5 nm. Water dif-
found in a number of sources [18,24–27]. The purpose of Fig. 4 is fusion increases with water content in Nafion. However, there
to highlight the characteristic scattering length of ∼5 nm for Nafion has been minimal quantitative connections between the struc-
samples with absorbed water. There is no evidence of any scattering ture of Nafion determined by scattering experiments and transport
in the nm range for proton exchanged Nafion membranes with- rates. We explore here the consistency of convective water trans-
out absorbed water. The other three samples correspond to water port through Nafion and the structure of the hydrophilic domains
absorption at saturation conditions: saturated vapor at room tem- determined from scattering experiments. It will be shown that con-
perature, saturated liquid at room temperature and saturated liquid vective water transport coupled with water sorption predicts water
at 100 ◦ C. The SAXS results for 1100 EW Nafion indicate a small
Fig. 4. Small angle X-ray scattering of Nafion 1110 membranes in saturated vapor,
Fig. 3. Water flux through different Nafion Membranes at 23 ◦ C. room temperature saturated liquid and saturated liquid at 100 ◦ C.
Q. Duan et al. / Journal of Membrane Science 392–393 (2012) 88–94 91
is convected through a hydrophilic “channel” network consisting of a substantial hydrostatic pressure difference (∼100 kPa) between
2.5 nm diameter water channels spaced 5.5 nm apart; this structure the anode and cathode.
shows quantitative agreement with the results from SAXS. Benziger and co-workers, and Monroe et al. concluded that
interfacial water transport at the membrane vapor interface is
4.1. Effect of temperature and equivalent weight on hydraulic the principal resistance to water transport in pervaporation sys-
permeability tems [1,8,20]. Because the limiting transport resistance is at the
vapor/membrane interface, the water activity in the membrane is
Two recent papers have reported measurements of pressure nearly constant across the membrane, approximately equal to the
driven water convection through Nafion. Weber and collaborators liquid water activity, as shown by Eq. (3), where km is a function of
from Toyota reported permeability coefficients for Nafion 211 and temperature.
Nafion 212 [2]. Their values for 1100 EW Nafion is in the range vapor liquid vapor
(Qpervaporation ) = km (amembrane − aw ) ≈ km (aw − aw ) (3)
of 1–8 × 10−16 cm2 very close to those reported here at 60 and w
80 ◦ C. The permeability they measured at 25 ◦ C was 4 times smaller Saturated liquid activity is unity (aw
saturated liquid
= 1). The activity
than the value we report. Holdcroft and co-workers also measured correction for a pressurized liquid is given by the Poynting correc-
hydraulic water permeability through Nafion 212 [4,5,21]. They tion shown in Eq. (4) (assuming that liquid water is incompressible
also obtained values circa 10−16 cm2 similar to those reported here. over the pressures of interest).
These recent values are almost 100 times less than earlier values
reported by Bernaradi and Verbrugge [17]. We suspect there were P sat )V̄
sat V̄w (P − Pw w
some difficulties with those early experiments. aw = aw (Pw ) + exp dP = 1 + exp
sat RT RT
Hydraulic permeabilities at 23 ◦ C were almost the same for Pw
N115, N1110 and N212, all of which have an equivalent weight sat )V̄
(P − Pw w
of 1100. These three membranes also sorbed the same number of ≈1+ (4)
RT
water molecules per sulfonic acid groups ( = 21H2 O/SO3 at 23 ◦ C).
The hydraulic permeability of N1035, with EW 1000, is greater than The activity correction to pressurized water at 100 ◦ C from satu-
the permeability of the 1100 EW Nafion membranes. ration (0.1 MPa) to 1 MPa pressure (10 bar) is ∼0.001. Hence, we
Our results, as well as those of Kientiz et al. and Adachi et al., conclude that at low to moderate differential pressures no mea-
found that the hydraulic permeability increased with tempera- sureable change to the water pervaporation flux is expected. This
ture. In all three studies the water flux increased more than that is consistent with pressurized pervaporation experiments by Kien-
predicted by the decrease of water viscosity with temperature, indi- tiz et al. and Adachi et al. (We did similar experiments. Initially
cating that the hydraulic permeability increased with temperature. we observed a small change in the steady state flux for pressur-
Results in Table 1 also show that the number of water molecules ized pervaporation through Nafion. However, when we followed
sorbed per sulfonic acid group increased with temperature, indi- the flux dynamically we discovered the change in flux was due to
cating that the volume fraction of water in Nafion increased with bowing of the membrane due to the pressure differential, which
increasing temperature. The increase in hydraulic permeability increased the interfacial area.)
with temperature and equivalent weight is greater than expected There is no convective water flux across the membrane/vapor
from the increased volume fraction of water. The water volume interface. Since interfacial transport at the vapor/membrane inter-
fraction, ϕw , given in Eq. (2) changes by almost 10% while the face is the limiting resistance to pervaporation, any contribution
hydraulic permeability increased by 50–80%. This difference sug- to water transport by hydraulic permeation in the membrane will
gests there may be structural changes to the hydrophilic domains increase the water concentration at the membrane/vapor inter-
with increased water sorption beyond simple volume expansion. face and reduce the already small water activity gradient across
the membrane.
(Nafion /EW)Vw When liquid water is at both membrane surfaces the interfa-
ϕw = (2)
1 + (Nafion /EW)Vw cial transport resistances are negligible. Unless there is a pressure
(or temperature) gradient across the membrane there is no driv-
4.2. Hydraulic permeation vs. pervaporation ing force for water transport. A differential pressure across the
membrane will drive water transport by diffusion and hydraulic
The recent paper by Kientiz et al. compared the water fluxes permeation. Diffusive permeation is driven by the water activity
from liquid/vapor pervaporation and liquid/liquid hydraulic per- gradient across the membrane. The activity difference for pressur-
meation. They observed that the liquid/vapor pervaporation fluxes ized liquid water on both sides of the membrane is given by the
were significantly greater than the liquid/liquid hydraulic perme- Poynting correction shown in Eq. (5).
ation fluxes. Kientiz et al. suggested that hydraulic permeation Pcathode
could be neglected relative to the pervaporation if there was an V̄w (Panode − Pcathode )V̄w
aw = exp dP = exp
activity gradient [2]. Adachi et al. also made similar observations Panode
RT RT
[4]. In our liquid/vapor permeation experiments in our labs we
also observed larger pervaporation water fluxes than the convec- (Panode − Pcathode )V̄w
≈ (5)
tive water fluxes we report here [1,20,32]. Is hydraulic permeation RT
important to water transport in Nafion? The diffusive water flux (Qw,diffusive ) associated with the hydro-
Water transport across Nafion membranes is essential to both static pressure difference across the membrane of thickness tm , is
membrane humidifiers and PEM fuel cells. The water activity dif- given by Eq. (6); where Dw is the diffusion coefficient of water and
ferences across the membrane are quite different in fuel cells cw is the concentration of water in the membrane (cw = NSO3 =
compared to membrane humidifiers. Nafion membrane humid- Nafion /EW where NSO3 is the density of sulfonic acid groups in
ifiers operate as pervaporation cells with a small hydrostatic Nafion). Diffusion coefficients for 1100 EW Nafion were reported
pressure difference (<10 kPa) but large relative humidity difference by Zhao et al. [20]; Dw (aw = 1) ≈ 5 × 10−6 cm2 s−1 .
across the membrane [40–42]. In contrast, fuel cells have saturated
liquid/gas streams at both sides of the membrane throughout most aw Dw NSO3 (Panode − Pcathode )V̄w
Qw,diffusive ≈ Dw cw,mem = (6)
of the fuel cell; there is a negligible relative humidity difference, but tm tm RT
92 Q. Duan et al. / Journal of Membrane Science 392–393 (2012) 88–94
The ratio of the diffusive flux (Eq. (6)) to the convective flux (Eq.
(1)) with liquid present on both sides of the membrane is given by
Eq. (7).
Table 2
Pore network parameters for liquid water flow in Nafion.
overcome the viscous drag with the walls of the channels. The The results indicate that the spacing between hydrophilic
flow rate as a function of pressure drop may be approximated by domains, d, ranges from 5 to 6 nm, increasing with water
Poiseuille flow (Eq. (10)), where laminar flow in uniform square volume fraction. Those values agree with the characteristic dis-
channels with hydraulic radius rh is assumed. tance observed from scattering experiments (e.g. see Fig. 4).
The hydrophilic channel diameter, dchannel = 2a, is approximately
rh2 P
Qw,pore = (2rh )2 (10) 2.3–2.7 nm.
8 Lpore The pore structure suggested here is similar to that previous
proposed by Gebel and Diat for proton transport in Nafion [48,51].
The total water flow for channels spaced at a distance d apart is
Gebel and Lambard had previously combined water sorption data
given by Eq. (11). To account for distortions of the real pore network
with the characteristic dimension from SAXS experiments to pre-
from the idealized model the effective length of the channels is
dict hydrophilic domain sizes and spacing [51]. The agreement of
given by the membrane thickness multiplied by a tortuosity factor,
the water sorption data and Porod analysis from Gebel and co-
.
workers was not very good assuming spherical domains. The fibril
(2rh )2 rh2 P rh4 P structure of hydrophobic cores surrounded by a hydrophobic shell
Qw = = (11)
d2 8 Lpore d2 2tm more recently proposed by Gebel and co-workers was more con-
sistent with scattering results and sorption data and we show here
Eqs. (10) and (11) assume that the Poiseuille flow description of it is also consistent with transport data.
liquid flow through cylindrical channels can be extended to more The water sorption and hydraulic water transport are not con-
complex geometries, this assumption has been validated for both sistent with models that suggest the hydrophilic pores are ∼5 nm
gas and liquid flow through porous materials, leading to the com- in diameter [56]. The flow results are also not consistent with the
monly employed Kozeny equation for flow through porous media classical Gierke model of spherical clusters connected by narrow
[58]. channels. If there were narrow channels between large spher-
The hydraulic radius accounts for the volume available for flow ical clusters the hydraulic permeability of the pores would be
divided by interfacial area over which the shear forces are exerted, greatly reduced, which would require the spacing between pores
as given by Eq. (12). The hydrophilic volume is the volume fraction to be reduced. The flow rate at fixed pressure increases with the
of water sorbed into the polymer membrane, given by Eq. (2). hydraulic radius raised to the 4th power, so a small decrease in
hydrophilic volume/unit volume ϕw channel radius would require more closely spaced hydrophilic
rh = = (12) channels.
interfacial area/unit volume ˛int
The interfacial area between the hydrophilic domains and the
hydrophobic matrix is not directly accessible for measurement.
However, the interfacial area is related to the hydrophilic network
parameters a and d, and is given by Eq. (13). Eq. (13) only includes 5. Conclusions
the interfacial area of the struts in the direction of flow.
Hydraulic permeation of water through Nafion membranes has
˛int = 24a(d − 2a) (13) been examined for different equivalent weights at temperatures
20–80 ◦ C. The principal findings are:
The hydraulic radius can also be expressed as a function of the
hydrophilic network parameters as given by Eq. (14).
3ad − 4a2
rh = (14) 1. Hydraulic permeation decreases with increasing membrane
3(d − 2a)
thickness.
Eqs. (2) and (11)–(14) can be combined to determine a and d 2. Hydraulic permeation increases with increasing temperature.
as functions of the experimentally measured and water volume 3. Hydraulic permeation increases with decreasing equivalent
fraction (ϕw ) and water flow rate (Qw ). weight of Nafion.
The water volume fractions were determined from water sorp- 4. Hydraulic permeation is of negligible importance for water per-
tion data and the results are listed in Table 2. From Eqs. (1) and vaporation; the increase of liquid water activity with pressure is
(11) the experimental permeability can be related to the hydraulic small.
radius and spacing between pores. 5. Hydraulic permeation is the dominant transport process for
water when liquid water is present on both sides of a Nafion
rh4 membrane.
= [2kw ] (15)
d2 6. Liquid water removal from the cathode catalyst layer is primarily
Assuming = 2 from the measurements of Zhao et al. [20] values through the cathode GDL.
of a and d were determined for each membrane at the different 7. Water sorption and hydraulic permeation results suggest a
temperatures using Eqs. (9) and (15); the results are summarized hydrophilic pore network in Nafion with hydrophilic domains
in Table 2. ∼2.5 nm in diameter spaced 5.5 nm apart.
94 Q. Duan et al. / Journal of Membrane Science 392–393 (2012) 88–94
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